CN1107672C - Process for preparing pyrazole derivatives - Google Patents

Process for preparing pyrazole derivatives Download PDF

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CN1107672C
CN1107672C CN98803283A CN98803283A CN1107672C CN 1107672 C CN1107672 C CN 1107672C CN 98803283 A CN98803283 A CN 98803283A CN 98803283 A CN98803283 A CN 98803283A CN 1107672 C CN1107672 C CN 1107672C
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CN1250440A (en
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P·W·纽瑟姆
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Bayer LLC
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Rhone Poulenc Agrochimie SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/38—Nitrogen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/63—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C255/65—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C317/30—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of rings other than six-membered aromatic rings of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
    • C07C317/48—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/16—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms

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  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
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  • Environmental Sciences (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

The invention relates to a process for preparing compounds having formula (IV), wherein R3, R4, R6 and Ar are as defined in the description, by reaction of a compound of formula (I) with a compound of formula (II) according to reaction scheme. The compounds of formula (IV) are useful as pesticides.

Description

Be used to prepare the intermediate of pyrazole derivatives
The present invention relates to insecticide active substance and intermediates preparation thereof.More specifically, the present invention relates to the preparation method of 1-aryl substituted pyrazolecarboxylic.
In the document of this analog derivative of preparation, many preparation methods have been described, as in International Patent Application WO 87/03781, WO93/06089 and WO94/21606; European patent application 0295117,0403300,0385809 and 0689650; United States Patent (USP) 5232940 and 5236938; In German publication application 19511269.
The known in the literature Japp-Klingemann reaction of looking back in organic reaction (Org.React.) the 10th volume 143-178 (1959) from 1887 is a kind of method by diazonium salt and activity methene compound prepared in reaction phenylazo compound.The phenylazo compound generally need not separate, but reacts with the alkali original place, loses a leavings group, and forms corresponding hydrazone.When phenylazo intermediate suitably replaces, spontaneous cyclization just takes place, produce 3,5-two replacement-4-proton-pyrazoles (promptly 3, the unsubstituted pyrazoles of 5-two replacement-4-).If desired 3,4, the trisubstituted pyrazoles of 5-, step afterwards needs further to handle.
An object of the present invention is to provide the new preparation method of arylpyrazole derivative.
Another object of the present invention provides a simple preparation method, as might be simpler than existing method.
These purposes are satisfied whole or in part by the present invention.
The invention provides and be used for directly preparation 3,4, the new more effective ways of 5-three replacement-1-arylpyrazoles.Now be surprisingly found out that, when carrying out the pyrazoles ring cyclisation of some arylazo intermediate, make leavings group (the generally leavings group that in this class reaction, loses) remerge C-4 place, can form 3 thereby produce into pyrazoles, 4,5-is trisubstituted-the 1-arylpyrazole.This just produces can reduce to prepare has 3,4 of required insecticidal activity, the number of reaction stages purpose advantage that 5-three replacement-1-arylpyrazole derivatives are required, and this means again when these compounds of preparation can produce less chemical waste, but and save energy.This also helps to reduce the cost that preparation has the 1-arylpyrazole derivative of insecticidal activity.
The invention provides a kind of method of the 1-of preparation arylpyrazole,
Figure C9880328300041
In the formula
Ar is the phenyl of selectivity replacement or the pyridyl that selectivity replaces;
R 3Be-C (O) R 8,-CN ,-CO 2H ,-C (O) NHR 8,-CHO ,-C (O) CO 2R 8,-S (O) mR 8,-C (O) CH 2Het, Het ,-C (O) CH 2R 9,-C (O) (C 1-C 6Alkyl) ,-C (O) (C 1-C 6Haloalkyl) ,-C (O) styryl, halogen ,-C (O) OR 8,-P (O) (OR 8) 2,-P (S) (OR 8) 2,-NO 2, R 9Or-S (O) mStyryl;
R 4Except that do not comprise-CN and halogen and R 3Definition identical;
M is 0,1 or 2;
R 6Be-NH 2,-OH or-CH 3
R 8Be C 1-C 6Alkyl, C 1-C 6Haloalkyl, R 9Or Het;
Het is 5 yuan or 6 yuan of heterocycles, and described heterocycle contains the identical or different heteroatoms that 1-3 is selected from nitrogen, sulphur or oxygen, and each carbon atom of described heterocyclic is unsubstituted or by halogen, C 1-C 6Alkyl, C 1-C 6Haloalkyl, C 1-C 6Alkoxyl group, C 1-C 6Halogenated alkoxy, cyano group, nitro, amino, N-(C 1-C 6Alkyl) amino, N, N-two (C 1-C 6Alkyl) amino, OH ,-S (O) m(C 1-C 6Alkyl) or-S (O) m(C 1-C 6Haloalkyl) replaces; And
R 9Be selected from halogen, C 1-C 6Alkyl, C 1-C 6Haloalkyl, C 1-C 6Alkoxyl group, C 1-C 6Halogenated alkoxy, cyano group, nitro, amino, N-(C 1-C 6Alkyl) amino, N, N-two (C 1-C 6Alkyl) amino, OH ,-S (O) m(C 1-C 6Alkyl) or-S (O) m(C 1-C 6Haloalkyl) phenyl that one or more group selectivity replace;
Described method comprises:
(a) make the compound of general formula (I) and the compound reaction of general formula (II) produce corresponding general formula (III) compound:
Ar-N≡N +X -
(I)
In the formula (I) definition of Ar as mentioned above, X is compatible negatively charged ion, R in the formula (II) 3And R 4Definition as mentioned above, R 5Be-CN ,-C (O) OR 8Or-C (O) (C 1-C 6Alkyl), R 9 R in the formula (III) 3, R 4, R 5With the definition of Ar as mentioned above;
(b) general formula (III) compound that makes is reset, produced corresponding general formula (IV) compound.
In this manual, following term has following general sense:
" alkyl " is the branched-chain or straight-chain alkyl that contains 1-6 carbon atom;
" haloalkyl " is the branched-chain or straight-chain alkyl that contains 1-6 carbon atom and one or more halogens, and described halogen can be identical or different;
" alkoxyl group " is side chain or the straight chain alkoxyl group that contains 1-6 carbon atom;
" halogenated alkoxy " is side chain or the straight chain alkoxyl group that contains 1-6 carbon atom and one or more halogens, and described halogen can be identical or different;
Halogen is meant fluorine, chlorine, bromine or iodine.
In above-mentioned definition, be to be understood that R 4Can not represent-CN or halogen, because in above-mentioned general formula (III) ,-CN or halogen can not be moved in rearrangement step on the adjacent carbon atom, produce the compound of above-mentioned general formula (IV).
X can be any negatively charged ion compatible with the common reactant condition.The example of proper group comprises (HSO 4), halogen, (BF 4), (ZnCl 3) and (CoCl 3).Preferred X is halogen or (HSO 4).
When Ar was phenyl, it had 0-5 substituting group.When Ar was pyridyl, it had 0-4 substituting group.Ar better has 1-3 substituting group.In any case, optionally the Ar substituting group better is selected from halogen, CN, NO 2, haloalkyl, halogenated alkoxy, S (O) mCF 3, SF 5And R 10, wherein m is identical with above-mentioned definition, R 10Identical with following definitions.
Ar better is the group with following general formula:
Figure C9880328300061
In the formula:
Z represents trivalent nitrogen atom or C-R 7Group, three valence links of other of this carbon atom constitute the part of aromatic ring;
R 1And R 7Represent hydrogen or halogen atom or CN or NO separately 2
R 2Represent halogen, haloalkyl, halogenated alkoxy, S (O) mCF 3, SF 5Or R 10
And R 10Be that 1-5 substituent phenyl arranged, described substituting group is selected from halogen, alkyl, haloalkyl, cyano group alkyl, cyano group, nitro, amino, diazanyl, alkoxyl group, halogenated alkoxy, halogenated alkyl carbonyl, formyl radical, alkyl-carbonyl, thiocarbamoyl, formamyl, alkoxy carbonyl, SF 5, or R 8S (O) m(the 4-bit substituent better is halogen, haloalkyl or halogenated alkoxy); Two adjacent phenyl substituents optionally connect into 1,3-Aden dialkylene (CH=CH-CH=CH-), methylene-dioxy (O-CH 2-O) or the halo methylene-dioxy (as-O-CF 2-O-), thus the ring adjacent formed with phenyl ring.
Below also be preferred implementation of the present invention, particularly when Ar is one of above-mentioned preferred group:
R 3Be-CN or-COR 8And/or
R 4For-S (O) mR 9,-S (O) mAlkyl or-S (O) mHaloalkyl; And/or
R 5Be-CN; And/or
R 6Be-NH 2
The various substituting groups of following numerical value provide representational general formula (I)-(IV) compound.In following table, " Ph " is meant phenyl, and " Pyr " is meant pyridyl; " Et " is meant ethyl.
Ar X R 3 R 4 R 5 R 6
2，6-Cl 2-4-CF 3Ph HSO 4 COCH 3 ?SO 2(4-ClPh) CN NH 2
2，6-Cl 2-4-CF 3Ph HSO 4 CN ?SO 2(4-ClPh) CN NH 2
2，6-Cl 2-4-CF 3Ph HSO 4 CN ?CO 2Et CN NH 2
2，6-Cl 2-4-CF 3Ph HSO 4 CN ?SOCF 3 CN NH 2
?2，6-Cl 2-4-CF 3Ph HSO 4 CN ?SOCF 3 CN NH 2
2，6-Cl 2-4-OCF 3Ph Cl Cl ?SOCF 3 CN NH 2
2，6-Cl 2-4-CF 3Ph HSO 4 CN ?SOEt CN NH 2
2，6-Cl 2-4-CF 3Ph HSO 4 CN ?P(O)(OEt) 2 CN NH 2
2，6-Cl 2-4-CF 3Ph Cl CN ?SOCF 3 CN NH 2
2，6-Cl 2-4-CF 3Ph HSO 4 SO(4-ClPh) ?COCH 3 CN NH 2
2，6-Cl 2-4-CF 3Ph HSO 4 CN ?COCF 3 CN NH 2
2，6-Cl 2-4-CF 3Ph HSO 4 CN ?NO 2 CN NH 2
2，6-Cl 2-4-CF 3Ph HSO 4 NO 2 ?COCH 3 CN NH 2
?2，6-Cl 2-4-CF 3Ph HSO 4 SO 2(2-thienyl) ?COCH 3 CN NH 2
2，6-Cl 2-4-CF 3Ph HSO 4 COCH 3 ?SO 2(2-thienyl) CN NH 2
2，6-Cl 2-4-(4-ClPh)Ph HSO 4 CN ?SOCF 3 CN NH 2
2，6-Cl 2-4-CF 3Ph HSO 4 Br ?COCH 3 CN NH 2
2，6-Cl 2-4-CF 3Ph HSO 4 Br ?COPh CN NH 2
2，6-Cl 2-4-CF 3Ph HSO 4 CN CO (2-furyl) CN NH 2
2，6-Cl 2-4-CF 3Ph HSO 4 CN ?SOCF 3 CN NH 2
2，6-Cl 2-4-SF 3Ph HSO 4 COCH 3 ?SO 2(4-ClPh) CN NH 2
2，6-Cl 2-4-SF 3Ph HSO 4 CN ?SO 2(4-ClPh) CN NH 2
2，6-Cl 2-4-SF 3Ph HSO 4 CN ?CO 2Et CN NH 2
2，6-Cl 2-4-SF 3Ph HSO 4 CN ?SOCF 3 CN NH 2
2，6-Cl 2-4-SF 3Ph HSO 4 CN ?SOCH 3 CN NH 2
2，6-Cl 2-4-SF 3Ph Cl Cl ?SOCF 3 CN NH 2
2，6-Cl 2-4-SF 3Ph HSO 4 CN ?SOEt CN NH 2
2，6-Cl 2-4-SF 3Ph HSO 4 CN ?P(O)(OEt) CN NH 2
2，6-Cl 2-4-(4CF 3Ph)Ph HSO 4 CN ?SOCF 3 CN NH 2
2，6-Cl 2-4-(4-OCF 3Ph)Ph HSO 4 CN ?SOCF 3 CN NH 2
2，6-Cl 2-4-OPh HSO 4 CN ?SOCF 3 CN NH 2
2，6-Cl 2-4-(4-SCF 3Ph)Ph HSO 4 CN ?SOCF 3 CN NH 2
Method of the present invention is generally carried out in two steps, though also can be undertaken by the continuation method that comprises general formula (III) compound original position rearrangement generation general formula (IV) compound.When this method component part manufacture method, this in-situ method may be preferred, because can avoid separating the intermediate of general formula (II) like this.
In the first step, in solvent, make diazonium salt (I) and compound (II) reaction, protonic solvent (as methyl alcohol, ethanol and acetate) is preferred.
This reaction preference ground produces azo-compound (III) in the presence of alkali, carry out in 0-120 ℃ temperature (0-25 ℃ more fortunately).When using alkali in this step, described alkali can be organic bases (as pyridine or triethylamine) or mineral alkali (as salt of wormwood or sodium hydroxide).During use, the consumption of alkali is generally 1-25 equivalent (by the molar equivalent of general formula (I) compound), is the 1-5 equivalent preferably.
In second step of this reaction sequence, azo-compound (III) is dissolved in the suitable solvent, optionally add alkali up to 20 equivalents (better up to 5 equivalents), produce the rearrangement pyrazoles of general formula (IV).The temperature of this step reaction is 0-120 ℃, is preferably 0-25 ℃.Solvent can be protonic solvent (as methyl alcohol, ethanol or an acetate), or better is aprotic solvent (as methylene dichloride, tetrahydrofuran (THF) or toluene).Suitable alkali can be organic bases (as pyridine, triethylamine or piperidines), mineral alkali (as sodium hydroxide, salt of wormwood or sodium hydride) or organo-metallic alkali (as potassium tert.-butoxide, sodium methylate, diisopropylamino lithium).Organic bases or organo-metallic alkali are preferred.
Above-mentioned general formula (III) compound generally is a molar excess, better adds general formula (III) compound of 1-2 mole, more preferably the 1.05-1.1 mole.
Above-mentioned general formula (III) (Ar, R in the formula 3, R 4And R 5Identical with above-mentioned definition, prerequisite is to work as R 3And R 5When all being cyano group, R 4Not-C (O) OR 8) compound is new, so it constitutes a part of the present invention.
General formula (II) compound can be by logical formula V compound and general formula R in the presence of alkali 5CH 2L (R in the formula 5Identical with above-mentioned definition, L is a leavings group) compound reaction makes:
R 3-CH 2R 4
(V) R in the formula 3And R 4Identical with above-mentioned definition.The example of suitable leavings group comprises halogen and tosylate (better being halogen).Above-mentioned alkali generally is highly basic (as sodium hydride or n-Butyl Lithium), this reaction general under-78 to 0 ℃ temperature and in aprotic solvent (as tetrahydrofuran (THF)) carry out.General formula (II) (R in the formula 5Be cyano group, R 3And R 4Identical with above-mentioned definition, prerequisite is to work as R 3Be-during CN, R 4Not-C (O) OR 8) compound also is novel, therefore constitutes another part of the present invention.
The embodiment of following indefiniteness further specifies the present invention.
Embodiment 1
Preparation 3-(4-chlorobenzene alkylsulfonyl)-4-cyano group fourth-2-ketone
In 300 milliliters of reaction flasks, add 2.4 gram (59.3 mmole) sodium hydride (60% dispersion in the oil) and 10 milliliters of hexanes.Removing hexane with transfer pipet also replaces with 60 milliliters of exsiccant tetrahydrofuran (THF)s (THF).Suspension is cooled to-15 ℃, and in 20 minutes, adds the solution of 12.0 gram (51.6 mmole) 4-chlorobenzene alkylsulfonyl acetone in 50 milliliters of THF, keep temperature of reaction to be lower than-12 ℃ simultaneously with dropping funnel.From cryostat, take out the yellow solution that forms, at room temperature stirred then 30 minutes.This solution is cooled to-5 ℃ again, drips 3.8 milliliters of (54.1 mmole) bromo acetonitriles with dropping funnel.After 5 minutes, from cryostat, take out this reaction mixture, at room temperature stir and spend the night.Make the reaction quencher with 1 milliliter of saturated sodium-chloride, reaction mixture is transferred in the separating funnel that contains 100 mL of saline with 100 milliliters of methylene dichloride.Separate organic layer, water layer is used 50 milliliters of dichloromethane extractions once again.The organic phase that merges with dried over sodium sulfate is filtered then, concentrates, and uses 1: 1 hexane then: methylene dichloride carries out silica gel column chromatography to be separated.Separate to obtain 8.2 gram (productive rate is 59%) 3-(4-chlorobenzene alkylsulfonyl)-4-cyano group fourth-2-ketone, a kind of is 90% yellow oil through the HPLC purity assay. 1H NMR (CDCl 3) show required product be main component: d7.6 (m, 4H), 4.42 (dd, 1H), 2.78 (m, 2H), 2.48 (s, 3H).
Embodiment 2
Preparation 3-(4-chlorobenzene alkylsulfonyl)-3-[(2,6-dichlor-4-trifluoromethyl phenyl) azo]-4-cyano group fourth-2-ketone
In 250 milliliters of reaction flasks, add 2.0 gram (35.7 mmole) potassium hydroxide particles, add 30 ml waters and 30 ml methanol then.In this solution, add 6.9 gram (25.5 mmole) 3-(4-chlorobenzene alkylsulfonyl)-4-cyano group fourth-2-ketone compounds.In case solution becomes gets evenly, in this reaction medium, once add 23.2 mmoles 2, the hydrogen sulfate diazonium salt of 6-dichlor-4-trifluoromethyl aniline.After at room temperature stirring 45 minutes, this reaction mixture is carried out aftertreatment by adding entry and methylene dichloride.After the layering, organic layer is stripped once with methylene dichloride (50 milliliters).With (Na 2SO 4) the dry organic phase that merges, filter, concentrate, then hexane: ethyl acetate mixture carries out silica gel column chromatography to be separated.Separate obtaining 5.1 gram (43%) title product, be glassy semisolid.HPLC shows that purity is 98%, 1HNMR be indicated as required product: d7.6 (m, 4H), 7.65 (s, 2H), 3.3 (dd, 2H), 2.42 (s, 3H).
Embodiment 3
Preparation 3-ethanoyl-5-amino-4-(4-chloro-phenyl-) alkylsulfonyl-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles
At 0.51 gram (1.0 mmole) 3-(4-chlorobenzene alkylsulfonyl)-3-[(2,6-two chloro-4-trichloromethyl phenyl) azo]-4-cyano group fourth-2-ketone is dissolved in and drips two triethylamines in the solution of 10 milliliters of methylene dichloride.After at room temperature stirring is spent the night, this reaction mixture is carried out aftertreatment by adding methylene dichloride again and washing with water.Separate organic layer, use dried over sodium sulfate, obtain 0.55 gram title compound after filtering and concentrating.HPLC shows that its purity is 94%, and fusing point is 158 ℃.
Embodiment 4
Preparation 2-(4-chlorobenzene alkylsulfonyl) succinonitrile
In 500 milliliters of reaction flasks, add 2.0 gram (51.0 mmole) sodium hydride (60% dispersion in the oil) and 20 milliliters of hexanes.Removing hexane with transfer pipet also replaces with 90 milliliters of exsiccant tetrahydrofuran (THF)s (THF).Suspension is cooled to-0 ℃, and in 10 minutes, adds the solution of 10.0 gram (46.4 mmole) 4-chlorobenzene alkylsulfonyl acetonitriles in 90 milliliters of THF, keep temperature of reaction to be lower than 12 ℃ simultaneously with dropping funnel.From cryostat, take out the solution that forms, at room temperature stirred then 40 minutes.This solution is cooled to 0 ℃ again, drips the solution of 3.4 milliliters of (48.7 mmole) bromo acetonitriles in 5 milliliters of THF with dropping funnel.After 5 minutes, from cryostat, take out this reaction mixture, at room temperature stirred two hours.Make reaction quencher and be condensed into oily matter with 1 milliliter of saturated sodium-chloride, with 150 milliliters of methylene dichloride reaction mixture is transferred in the separating funnel that contains 120 ml waters then.Tell organic layer and also wash again once, once with the washing of 120 mL of saline with 120 ml waters.Use the dried over sodium sulfate organic phase then, filter, concentrate, use 85: 15 hexanes then: ethyl acetate is carried out silica gel column chromatography and is separated.Separate obtaining 1.4 gram (productive rate is 12%) title compounds, be yellow powder.HPLC shows that its purity is 96%, and fusing point is 130-137 ℃.
Embodiment 5
Preparation 2-(4-chlorobenzene alkylsulfonyl)-2-(2, the 6-dichlor-4-trifluoromethyl) phenylazo succinonitrile
In 50 milliliters of reaction flasks, add 0.45 gram (1.77 mmole) 2-(the 4-chlorobenzene alkylsulfonyl) solution of succinonitrile in 15 ml methanol.In case solution becomes gets evenly, in this reaction medium, once add 1.61 mmoles 2, the hydrogen sulfate diazonium salt of 6-dichlor-4-trifluoromethyl aniline.After at room temperature stirring 45 minutes, this reaction mixture is carried out aftertreatment by adding salt solution and methylene dichloride.After the layering, with (Na 2SO 4) the dry organic layer that merges, filter, concentrate, then 90: 10 hexanes: ethyl acetate is carried out silica gel column chromatography and is separated.Separate obtaining 0.33 gram (42%) title compound, be the crystalline solid of redness. 19FNMR shows that its purity is more than 95%, and fusing point is 45-50 ℃.
Embodiment 6
Preparation 5-amino-3-cyano group-4-(4-chlorobenzene alkylsulfonyl)-1-(2,6-dichlor-4-trifluoromethyl phenyl) pyrazoles
In 0.3 gram (0.61 mmole) 2-(4-chlorobenzene the alkylsulfonyl)-solution of 2-(2, the 6-dichlor-4-trifluoromethyl) phenylazo succinonitrile in 20 milliliters of methylene dichloride, drip 3 triethylamines.After at room temperature stirring two hours, by this reaction mixture being carried out aftertreatment with the methylene dichloride dilution with water dispenser.After the layering, water with dichloromethane extraction once.The organic phase dried over sodium sulfate that merges is filtered, and concentrates, and carries out the silica gel column chromatography separation (with 90: 10 hexanes: eluent ethyl acetate).Separate obtaining 0.14 gram (productive rate is 47%) title compound, be orange foams.HPLC shows that its purity is 100%, and fusing point is 90-95 ℃.
Embodiment 7
Preparation 2,3-dicyano-2-(2, the 6-dichlor-4-trifluoromethyl) phenylazo ethyl propionate
The solution of 22.1 mmole dicyano ethyl propanoates in 20 milliliters of dehydrated alcohols is cooled to 0 ℃, in 15 minutes, adds 20.9 mmoles 2 then, the hydrogen sulfate diazonium salt of 6-dichlor-4-trifluoromethyl aniline with dropping funnel.Reaction mixture is warmed to room temperature, and stirs and spend the night.By adding entry and methylene dichloride this reaction mixture is carried out aftertreatment.After the layering, water layer is stripped once with methylene dichloride.The organic phase that merges is washed once with salt solution again, and the organic layer dried over sodium sulfate is filtered, and is concentrated, and with 90: 10 hexanes: ethyl acetate was carried out silica gel column chromatography.Separate obtaining 2.7 gram (33%) title compounds, be red viscosity oily matter, it contains 82% required azo product and 13% corresponding hydrazone. 1HNMR (CDCl 3) expression required product be main ingredient: d7.70 (s, 2H), 4.44 (m, 2H), 3.58 (q, 2H), 1.39 (t, 3H).
Embodiment 8
Preparation 5-amino-3-cyano group-1-(2,6-dichlor-4-trifluoromethyl phenyl)-4-ethoxycarbonyl pyrazoles
In 100 milliliters of reaction flasks, add 0.51 gram (1.30 mmole) 2, the solution of 3-dicyano-2-(2, the 6-dichlor-4-trifluoromethyl) phenylazo ethyl propionate in 20 milliliters of tetrahydrofuran (THF)s.Reaction mixture is cooled to-78 ℃, once adds 0.52 gram (1.30 mmole) sodium hydride (60% dispersion in the oil).Reaction mixture is warmed to ambient temperature overnight.In this reaction mixture, add 2 gram silica gel and 40 milliliters of ethyl acetate.Carry out after this slurry concentrated silica gel column chromatography (earlier with 90: 10 hexanes: ethyl acetate (1 liter) wash-out, afterwards with 80: 20 hexanes: ethyl acetate (2 liters) wash-out).Separating to obtain 0.16 gram (by purity is 82% raw material, and productive rate is 38%) solid, is 99% with its purity of HPLC analysis revealed, and fusing point is 201.5-202.5 ℃.
Embodiment 9
Preparation 2, the hydrogen sulfate diazonium salt of 6-dichlor-4-trifluoromethyl aniline
In 100 milliliters of reaction flasks, add 5.3 gram (23.2 mmoles) 2, the solution of 6-dichlor-4-trifluoromethyl aniline in 45 milliliters of Glacial acetic acid.This solution is placed in the ice-water bath and cools off, and once adds 3.8 gram (30.1 mmole) nitrosyl-sulfuric acids.From ice bath, take out this reaction mixture, at room temperature stirred 2 hours.The gained diazonium salt need not to purify and just can use.
General formula (IV) the compound useful as pesticides that makes with the inventive method.
Though preferred embodiment the present invention is described with reference to various, the those of skill in the art in this area only understand otherwise depart from spirit of the present invention and can carry out various changes, substitute, omit and change.Therefore, scope of the present invention is only limited by the scope of following claims, comprises its equivalent.

Claims (1)

1. compound is characterized in that it is:
3-(4-chlorobenzene alkylsulfonyl)-3-(2,6-dichlor-4-trifluoromethyl phenylazo)-4-cyano group fourth-2-ketone; Or
2-(4-chlorobenzene alkylsulfonyl)-2-(2, the 6-dichlor-4-trifluoromethyl) phenylazo succinonitrile.
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CN111825653A (en) 2019-04-19 2020-10-27 安道麦马克西姆有限公司 Preparation of substituted pyrazoles and use thereof as anthranilamide precursors
CN110483480A (en) * 2019-09-11 2019-11-22 江苏优普生物化学科技股份有限公司 The synthetic method of 2- (3- chloropyridine -2- base) -5- hydroxyl -3- pyrazolidinecarboxylate
CN110981806A (en) * 2019-12-06 2020-04-10 江苏优普生物化学科技股份有限公司 Method for synthesizing aryl pyrazole nitrile and byproduct carbonic acid diester
CN111592511A (en) * 2020-04-26 2020-08-28 衡水均凯化工有限公司 Preparation process of 4,4- (hexafluoroisopropenylidene) diphthalic anhydride
CN111592510A (en) * 2020-04-26 2020-08-28 衡水均凯化工有限公司 Synthesis method of 4,4- (hexafluoroisopropenylidene) diphthalic anhydride

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